Condensation product of the anthraquinone series and process of making same



Patented Feb. 12, 1935 *GOND'ENSATION" PRODUCT- OF, TH AN; THRAQUINONE-SERIES AND PROCESS OF MAKING .SAME

I {Ii- Heinz "Scheyer, '.Frankfort-on-the Main, Germany assign'or to General Aniline Works,:Inc.,

' J" "New 1911!, N. "Y5, a corporation of Delaware ,No' Drawing. Original, application September 21,

. 1931,;SeriaLNo. 564,157.' Divided and this application August 8,' 1933, Serial No. 684,288. In

Germanyoctober 18, 1930 as r e p mv e-fi l e n fiQfi k 5 51 flied e mb r 1931 and relating to a process for-producing con- 'densationproducts of the anthraguinone'series.

g present invention relates to new condensation products of the anthraquinone series and a process of making same. I v I 7 I h ve foundanew process for producing con:

densation productsof theanthraquinone series, which consists in'heating methyleneanthrone of the aQthraduinonejra dicles maycon t i mo v l ni u stit nt P h aforesaid kind. .-At temperatures (above 290i C advantageously with the addition of a' suitable diluent, solvent or fiuxing material, the products of the general Formula II are'transformed intofinal products.

The final products corresponding to theprobable formula:

wherein the anthraquinone radicles may contain a monovalentsubstituent of the aforesaid kind, are fully colored products which are soluble in the alkaline hydrosulfite vat and dye cotton therefrom fast shades. The fundamental body of this series itself is apparently identical with the 5.6.1l.12-dibenzoperylenequinone4.10 described in French Patent No. 601,856,-- dated 16th July 1925, and signified by the formula X on page 2 of the specification. 7

The assumption of the aforesaid formulae is supported by the-fact that in the second step of reaction the evolution of ethylene gas can be detected. By this course of the reaction the present process differs substantially from the condensaum reaction of such derivatives of methylene-- anthrone in'which one or both hydrogen atoms of themeso-standing 'rnethylenegroup are replacedby a phenylradicle. Whereas these products according to German Patents Nos. 451,907 and 454.,945enter an intramolecular condensation reaction in the present case apparently two molecules of methyleneanthrone arecombined. LThe second step of thereaction is' carried out by heating the primary reaction products cor responding probably" with'the aforesaid formula:

II at temperatures above 200 ,C..,' i. e. above their melting point. As examplesof suitable diluents, solvents or fluxing materials, which may be add ed, may bQHlGlItiOnd. ethylcarbazole, p-naphthol,

.an alkaline solution containing active chlorine orhydrogen peroxide.-

When using sulfuric acid, by simultaneous sul: V

A- mixture of 10 parts of 'methyleneanthron'e, about parts of methanol and about 10v parts fonation the corresponding sulfonic acid derivatives may be obtained .whichmay be used as'acid wool dyestuffs. v When using aluminium chloride as condensing agent, it is not necessary to isolate the inter-' mediates of Formula II, by increasing the temperature of the aluminium chloridefusion above 200 the final products are directly obtainable by starting from methyleneanthrone and its sub stitution products.

In order to isolate the intermediates of Formu-j la II the temperature of the aluminium chloride. fusion, which may be carried out by "adding a;

suitable diluent, such as sodium chloride, is to be held between about 100 to 200.. The products corresponding to Formula II are new compounds, they are nearly colorless and are soluble in concentrated sulfuric acid witha yellowish color, they are insoluble inalkalies, they melt above 200 C. under decomposition, while forming the products of Formula III.

When carrying out the first step of the reaction under mild conditions, i. e.practically by heating methylene-anthrone or its substitution products of the above described-kind in an acidic medium at temperatures below 100 C., it is possible to isolate a precedent intermediate, corresponding presumably to the formula:

wherein the anthraquinone radicles may contain a monovalent substituent of the above described type. These intermediates are likewise new compounds, they are intense. yellow colored and diifer from the products of Formula II by the fact that they dissolve 'in alcoholic aqueous alka lies with a yellowish red color.

In order to interrupt the series of condensati on-reactions at this first step one may heat methylene-anthroneand its substitution products with addition of, for instance, alcoholic hydrochloric, sulfuric acid or formic acid at temperatures below 100 C. 4

By heating these new products with anhydrous halides, such as aluminium chlorides, at temperatures between about 100 to 200 (3., the

- lowish" red color.

products of Formula II, by increasing the term perature above 200 C., directly the final prod ucts of the Formula III are obtained.

In order to further illustrate my invention the following examples are given, the parts being by weight and-all temperatures in centigrade degrees. But I wish it to beunderstood that I am not limited to the particularconditions or spep d mentioned the e -j H Example! of concentrated hydrochloric acid is boiled for sometime in an apparatus provided with a reifluxcondenser. Almost, immediately the coloration of the liquid turns to yellow and'a yellowish,

well crystallized, precipitate is formed. If a test of-the precipitate, dissolved in sulfuric acid, no

longerfshows 'the intense green fluorescence: of

methylen'eamthron, the formed precipitate is.

separated while hot from the liquor. The new.

product apparently corresponding with the: Formula IV or V dissolves in concentrated sulfuric acid with a yellow, in an aqueous'alcoholiccai1s tic alkali solution'with a yellowish red color;

The raw-product melts at about 240" ,C. By

shortly thereafter extracting 3 it with glacial acetic acid the new und may" The purified product melts at about""254"C.-

The same product is obtained-when heating a mixture of 10' parts of methyleneanthrone, about partsof concen ZOO-parts of "methanoliand '30 v trated sulfuric acidforabout 3 hours in an1ap'- paratus provided with a reflux condenser isolating the product asfdescribed above.

When heating the new compound with about the tenfold amountf'of aluminiumchloride with addition of sodium chloride while stirring at about C., substantially the further intermediate is formed, corresponding to Formula 11. When. increasing the temperature of the aluminiumchloride fusion above 200 C. orjwhen continuing the heating at temperatures below 200 C. for a long. time,;immediatelyin the main the dyestuif of Formula III is formed. a

, g 7 Example 2 rated while hot from the liquor. The product thus obtained is identical with the product'of the foregoing example. V

' Example 3 10 parts of methylene-2-chloranthrone are mixed with about 50' parts of glacial acetic acid and 12.5 parts of concentrated sulfuric acid and the mixture is heated in'a'n apparatus provided with a reflux condenser. The initialproduct is gradually dissolved and thenew condensation product separates inform of yellow crystals, which are separated from the. liquor and washed out. The new product dissolves in concentrated sulfuric acid ,withfan orange-yellow,'in an aque-" ous alcoholic causticfalkali solution with a yel-' The raw product melts at about 284 C. The new product corresponds probably with the formula:

I claim:

1. A process for producing condensation products of the anthraquinone series which comprises heating a Q-methylene-anthrone compound of the formula:

till 6 3 WWW 1| 0 wherein in one of the 1 to 8 positions a monovalent substituent selected from the class consisting of halogen, an alkyl-, aryl-, acylaminoand sulfonic acid group, may be present, with an acid condensing agent at temperatures below about C.

2. A process for producing condensation products of the anthraquinone series which comprises,

heating a Q-methylene-anthrone compound of the formula:

(5H2 FW/skfik 1/ 10 U wherein in the 2 position halogen may be present, with an acid selected from the group consisting of alcoholic hydrochloric and sulfuric acid and formic acid at temperatures below about 100 C.

3. Bimolecular condensation products of methylene-anthrone, corresponding with the formula:

in which the Xs mean hydrogen or halogen,

which products represent intense yellow colored crystalline substances, melting above 200 C. and being soluble in sulfuric acid with a yellowish, in aqueous alcoholic caustic alkalies solutions with a yellowish red coloration.

4. The bimolecular condensation product of methylene anthrone, corresponding with the formula:

which product dissolves in concentrated sulfuric acid with a yellow, in an aqueous alcoholic caus-v tic alkali solution with a yellowish red color, melting in a pure state at about 254 C.

5. The bimolecular condensation product of which dissolves in concentrated sulfuric acid with an orange-yellow, in an aqueous alcoholic caustic alkali solution with a yellowish red color, melting at about 284 C.

HEINZ SCHEYER. 

